Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
  • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
  • B01J8/382—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it with a rotatable device only
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G21/00—Compounds of lead
  • C01G21/02—Oxides
  • C01G21/10—Red lead [Pb3O4]

Definitions

• reaction rate must be proportional to the oxygen partial pressure, among other things.
• the higher the temperature the stronger the back reaction; the decomposition point for the red lead can, however, be shifted upwards by increasing the oxygen partial pressure in the ambient atmosphere, with all other steps influencing the reaction also being accelerated, of course.
• the latter method also includes the process described in IT-PS 485215, in which intimate contact between lead and oxygen is achieved by vaporization of the lead; here it was certainly the high energy consumption that did not help the otherwise very interesting process to spread.
• GB-PS 559 994 shows a red lead reactor in which the lead oxide is kept in motion by a vertical agitator and the preferably preheated oxidizing gases are introduced into the reactor from below, so that they are not only chemical with the material all the way to the surface react, but also help to keep the temperature of the material at a constant level.
• the oxidizing Also introduce gases under pressure, which has a remarkable effect on the reaction rate.
• this is a batch reaction, a batch at about 480 ° C. taking 8 hours to convert into a material with 90% P -, 0, which previously required 20 to 30 hours.
• US Pat. No. 3,450,503 shows a process for producing lead smoothness, which can then be oxidized to red lead in a second process step.
• the smoothness is produced by spraying molten lead in a zone of high gas turbulence and oxidizing it to lead smoothness with air or oxygen-enriched air, which can also be supplied with excess pressure.
• the finely dispersed PbO produced by this process which is known as the "Goldschmidf process" can then be oxidized in a deck oven to highly disperse red lead.
• the oxidation of lead which practically takes place in a fluidized bed, does not lead to red lead and the oxidation of lead smoothness to red lead takes place in a conventional manner.
• the object of the invention is a significant reduction in the reaction time of the oxidation of PbO to Pb.A. compared to known methods when achieving the at least the same Mennige quality, e.g. expressed in% Pb ⁇ ".
• Oxidation rate is particularly high when working in a fluid bed under certain conditions. It has been confirmed that in all these known technical processes - an exception may be the IT-PS 485215 and GB-PS 559 994 - there is a significant delay in reaction due to the fact that the oxygen is consumed within the solid bed and not can diffuse quickly enough so that there is actually a very low partial pressure on the particle surface by keeping the lead oxide to be oxidized in a stirrer reactor suspended by a stirrer like a fluidized bed, but it is essential that the amount of lead smoothness to be oxidized per Time unit is controlled appropriately.
• the object of the invention for the production of red lead with considerably greater speed than is currently possible is accordingly achieved in that the lead oxide to be oxidized is supplied with sufficient oxygen on the particle surface by only withdrawing part of the finished product from the finished oxidized fluidized bed and is replaced by new lead oxide to be oxidized.
• the method according to the invention based on the above findings also makes it possible to use the mechanical stirring energy introduced to keep the fluidized bed at the reaction temperature.
• the apparatus In all other methods of mine production, the apparatus must be constantly heated because it cannot be sufficiently insulated; The enthalpy of reaction and the heat of friction are lost.
• the reactor according to the invention on the other hand, it may even be necessary to cool the reaction in certain time intervals, which is a great advantage from a control point of view.
• a fluidized bed 5 is maintained by the agitator 2; When the reactor is started up, this consists of the finished product 4, which is presented. Hot air is blown into the reactor jacket 11 by means of the blower 12 via the air heater 13. In this way, the heating of the fluidized bed, which is also possible without hot air, is greatly accelerated. During the heating, air and / or oxygen is already supplied via the gas inlet tube 6 and the desired atmosphere is set. After the reaction temperature, which is measured with the thermocouple 10, has been reached, the heated finished product which has been heated up is partially discharged; it is expedient for productivity reasons not less than 25% and for thermal reasons expedient not to discharge more than 50% of the amount of the fluidized bed. About 35 to 45% is preferred. Immediately thereafter, the raw material 3 is charged via its cellular wheel sluice 8 in the same amount as the finished product was emptied. The fluidized bed 5 thus retains its mass and the drive motor of the agitator 2 retains its intended load.
• the temperature of the fluidized bed drops abruptly by up to 100 ° C, but rises very quickly, within 5 to 10 minutes, due to the exothermic enthalpy of reaction to the specified value, which is in the range of approx. 500 ° C.
• the filling of the reaction vessel must now be set so that the stirring energy and the gradually decreasing enthalpy of reaction lead to a further increase in temperature. However, this may only be done up to a certain target temperature, which is between 470 and 520 ° C, preferably around 500 ° C.
• a further increase is avoided in that the excess heat is removed by means of cooling air which blows the blower 12 through the jacket 11; a controller ensures that the target temperature only fluctuates by a few degrees in the further course of the batch.
• the batch duration now depends not only on the desired degree of oxidation but also on various other parameters such as raw material quality and Gas composition, i.e. the oxygen content of the injected gas.
• the oxygen content can fluctuate or be set between 21 and 100%. So you can also work with air.
• the batch duration must be determined experimentally, which is possible with a few experiments. As soon as the time found has expired, part of the finished product is withdrawn, as in the commissioning described, and then the corresponding amount of raw material is charged. The cycles can be continued for any length of time.
• the air heater 13 only has to be switched on for commissioning and in the event of any malfunctions. Since only a part of the finished product is drawn off and accordingly only a part of the preliminary product is charged, no external heating is required at this stage either, since, as mentioned above, the temperature rises very quickly to the specified value.
• the stirring speed is such that a fluidized bed-like state is always maintained, but can be set automatically, depending on whether one wishes to increase the temperature or maintain the temperature, faster or slower if only the fluidized bed is retained.
• stirring speeds 150 to 200 rpm, in particular 150 to 180 rpm, are expedient, while in a pilot plant reactor with a diameter of 400 mm, an agitator speed of approximately 360 rpm is required in order to achieve approximately the same peripheral speed.
• the atmosphere in the fluidized bed is adjusted to a desired oxygen potential by targeted gas supply.
• the easiest way to do this is by adjusting the oxygen content of the gas supplied, but also instead or additionally by varying the pressure.
• Red lead produced by the process according to the invention only needs to be ground if it is produced for painting purposes.
• the fineness is directly sufficient for use in the glass, ceramic and battery industries, since it is not particularly important in those applications.
• the invention also relates to the device for performing this method, as shown in the accompanying figure and described in connection with the method.
• This device consisting of the reaction vessel 1 with agitator 2, gas supply 6 and gas outlet 7 for the oxidizing gas and locks 8 for the supply of raw material and the removal of finished product in a device 10 for measuring the internal temperature, is characterized in that the reactor 1 is coated on all sides with good insulation 9 and has a cavity for an air jacket 11 around the reactor, this air jacket having an air supply and air discharge line and a blower 12 and an electric air heater 13 being arranged in the air supply line.
• the speed of the agitator 2 is controlled automatically as a function of the target temperature in the reactor by the schematically illustrated device 15 within predetermined limits, the limits being such that the a fluidized bed is still maintained at the lower limit of the number of revolutions and at the upper limit of the stirring speed there is still no noticeable erosion of the reactor.
• the heating or cooling of the air jacket 11 is also automatically controlled by the fan 12 in order to maintain a previously set temperature or to heat the reactor within a certain time via the air jacket 11 in addition to the heat of reaction.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Manufacture And Refinement Of Metals (AREA)

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Applications Claiming Priority (2)

Publications (1)

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• 1989
  • 1989-07-10 DE DE3922654A patent/DE3922654A1/de active Granted
• 1990
  • 1990-07-06 EP EP90910704A patent/EP0437562B1/de not_active Expired - Lifetime
  • 1990-07-06 WO PCT/EP1990/001094 patent/WO1991000848A1/de active IP Right Grant
  • 1990-07-06 DE DE9090910704T patent/DE59000334D1/de not_active Expired - Lifetime
  • 1990-07-06 US US07/655,450 patent/US5482689A/en not_active Expired - Fee Related
  • 1990-07-06 ES ES199090910704T patent/ES2035753T3/es not_active Expired - Lifetime

Patent Citations (2)

Non-Patent Citations (2)

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